TWI425532B - Process for producing zno varistor with higher potential gradient and non-coefficient value - Google Patents
Process for producing zno varistor with higher potential gradient and non-coefficient value Download PDFInfo
- Publication number
- TWI425532B TWI425532B TW100143801A TW100143801A TWI425532B TW I425532 B TWI425532 B TW I425532B TW 100143801 A TW100143801 A TW 100143801A TW 100143801 A TW100143801 A TW 100143801A TW I425532 B TWI425532 B TW I425532B
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- Taiwan
- Prior art keywords
- zinc oxide
- potential gradient
- oxide varistor
- varistor
- doped
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 57
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 313
- 239000011787 zinc oxide Substances 0.000 claims description 155
- 150000002500 ions Chemical class 0.000 claims description 46
- 239000013078 crystal Substances 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 35
- 238000005245 sintering Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 8
- 238000003980 solgel method Methods 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 238000009388 chemical precipitation Methods 0.000 claims description 6
- 238000007796 conventional method Methods 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000000593 microemulsion method Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 claims 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims 1
- -1 Sb 2 O 3 Inorganic materials 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 230000016507 interphase Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KAGOZRSGIYZEKW-UHFFFAOYSA-N cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Co+3].[Co+3] KAGOZRSGIYZEKW-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/105—Varistor cores
- H01C7/108—Metal oxide
- H01C7/112—ZnO type
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C04B35/624—Sol-gel processing
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
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- C04B35/628—Coating the powders or the macroscopic reinforcing agents
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
- C04B35/62818—Refractory metal oxides
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
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- C04B35/62821—Titanium oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
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- C04B35/62823—Zirconium or hafnium oxide
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Description
本發明涉及一種氧化鋅變阻器的製法，尤指一種使氧化鋅變阻器同時提高電位梯度及非線性係數的製法。The invention relates to a method for preparing a zinc oxide varistor, in particular to a method for simultaneously increasing a potential gradient and a nonlinear coefficient of a zinc oxide varistor.
氧化鋅變阻器具優異的非歐姆特性，是最佳的過電壓保護裝置，應用於電力或電路系統中作為保護元件的瞬態電壓抑制器使用，可以發揮防止瞬間突波及保護元件的效果。The excellent non-ohmic characteristics of the zinc oxide varistor are the best overvoltage protection devices. They are used in transient voltage suppressors used as protection elements in electric power or circuit systems to prevent transient surges and protect components.
然而，隨著世界各國對電力系統邁向超高壓輸電系統的規劃，氧化鋅變阻器必須具備高電位梯度(potential gradient)及高能量吸收特性，已成為重要的發展趨勢。However, with the planning of power systems in the world for UHV transmission systems, zinc oxide varistor must have a high potential gradient and high energy absorption characteristics, which has become an important development trend.
眾所周知，氧化鋅變阻器的電位梯度與單位厚度中的氧化鋅晶界數量有關，亦即單位厚度中氧化鋅晶粒越小，則晶界數越多，其電位梯度也越大。經典理論認為，氧化鋅晶界的擊穿電壓約為3V/1晶界。而且，氧化鋅變阻器的非歐姆特性，是緣於兩個氧化鋅晶粒之間所形成的雙肖特基勢壘，提高勢壘的高度，即可提高氧化鋅變阻器的非線性係數和氧化鋅晶界的擊穿電壓。It is well known that the potential gradient of a zinc oxide varistor is related to the number of zinc oxide grain boundaries per unit thickness, that is, the smaller the zinc oxide grains per unit thickness, the larger the number of grain boundaries, and the larger the potential gradient. According to classical theory, the breakdown voltage of zinc oxide grain boundaries is about 3V/1 grain boundary. Moreover, the non-ohmic property of the zinc oxide varistor is due to the double Schottky barrier formed between the two zinc oxide grains, and the height of the barrier is increased to increase the nonlinear coefficient of the zinc oxide varistor and the zinc oxide. Breakdown voltage of the grain boundary.
但，使用傳統配方與工藝所製備的氧化鋅變阻器，其電位梯度僅為180～200V/mm，能量耐受密度為100～140J/cm3 ，不適合應用於超高壓輸電系統的線路上。However, the zinc oxide varistor prepared by using the conventional formula and process has a potential gradient of only 180 to 200 V/mm and an energy withstand density of 100 to 140 J/cm 3 , which is not suitable for application on the line of the ultrahigh voltage transmission system.
因此，為了研製具高電位梯度的氧化鋅變阻器，現有技術所使用的方法，可以歸納以下二個方面：Therefore, in order to develop a zinc oxide varistor with a high potential gradient, the methods used in the prior art can be summarized into the following two aspects:
一、在氧化鋅晶體的摻雜離子中，添加稀土類氧化物成分，結果所製得的氧化鋅變阻器的電位梯度提高至400V/mm；1. Adding a rare earth oxide component to the doped ions of the zinc oxide crystal, and as a result, the potential gradient of the obtained zinc oxide varistor is increased to 400 V/mm;
二、改進氧化鋅陶瓷粉的製備工藝或是引入新工藝，例如，引入高能球磨工藝或奈米製粉工藝，結果所製得的氧化鋅變阻器的電位梯度提高至2,000V/mm。Second, improve the preparation process of zinc oxide ceramic powder or introduce a new process, for example, introducing a high-energy ball milling process or a nano-milling process, and as a result, the potential gradient of the obtained zinc oxide varistor is increased to 2,000 V/mm.
但，上述對氧化鋅變阻器提高電位梯度的現有技術，卻出現氧化鋅變阻器的電位梯度一旦提高，而其非線性係數卻下降的缺點。這對氧化鋅變阻器的性能，尤其是對氧化鋅變阻器的限壓效果影響很大。However, the prior art for increasing the potential gradient of the zinc oxide varistor has the disadvantage that the potential gradient of the zinc oxide varistor is increased and the nonlinear coefficient is decreased. This has a great influence on the performance of the zinc oxide varistor, especially the pressure limiting effect of the zinc oxide varistor.
有鑑於此，本發明的主要目的在於提供一種氧化鋅變阻器的製法，包括：先預製充分半導化的摻雜氧化鋅晶粒，然後再與預製的晶間相組分混合，最後通過燒結過程所製得的氧化鋅變阻器，具有同時提高氧化鋅變阻器電位梯度及非線性係數的特點。In view of this, the main object of the present invention is to provide a method for preparing a zinc oxide varistor, comprising: pre-preparing a sufficiently semi-conductive doped zinc oxide crystal grain, then mixing with a pre-formed intercrystalline phase component, and finally passing through a sintering process. The obtained zinc oxide varistor has the characteristics of simultaneously increasing the potential gradient and nonlinear coefficient of the zinc oxide varistor.
本發明的製法，與氧化鋅變阻器習知製法的差異，主要在於將製備充分半導化的摻雜氧化鋅晶粒，與製備高阻抗的燒結粉或玻璃粉(又稱晶間相組分)，分為二個獨立工序來製備，且獲致下列意想不到的優點，而突破了氧化鋅變阻器習知製法的限制，故所製得的氧化鋅變阻器兼具高電位梯度與高非線性係數：The difference between the preparation method of the present invention and the conventional method for preparing a zinc oxide varistor is mainly to prepare a sufficiently semi-conductive doped zinc oxide crystal grain, and to prepare a high-resistance sintered powder or glass powder (also referred to as an intergranular phase component). It is divided into two separate processes to prepare, and the following unexpected advantages are obtained, and the limitation of the conventional method of the zinc oxide varistor is broken. Therefore, the obtained zinc oxide varistor has both a high potential gradient and a high nonlinear coefficient:
1.提高氧化鋅晶粒之間的肖特基勢壘高度；1. Increasing the Schottky barrier height between zinc oxide grains;
2.增加單位厚度中的氧化鋅晶粒之間的晶界數；2. Increasing the number of grain boundaries between the zinc oxide grains in the unit thickness;
3.提高組分與結構的均勻性。3. Improve the uniformity of components and structure.
本發明的氧化鋅變阻器製法，適用於製造具超高電位梯度及非線性係數的氧化鋅變阻器，優選用途是用於製造電位梯度介於1200～9000V/mm、非線性係數α介於21.5～55及漏電流IL 介於1～21μA的氧化鋅變阻器；最佳用途是用於製造電位梯度超過2000V/mm的氧化鋅變阻器。The method for preparing a zinc oxide varistor of the invention is suitable for manufacturing a zinc oxide varistor with an ultra-high potential gradient and a nonlinear coefficient, and the preferred use is for manufacturing a potential gradient between 1200 and 9000 V/mm, and a nonlinear coefficient α ranging from 21.5 to 55. And a zinc oxide varistor with a leakage current I L between 1 and 21 μA; the best use is for a zinc oxide varistor with a potential gradient exceeding 2000 V/mm.
本發明的氧化鋅變阻器製法，包括以下步驟：The method for preparing a zinc oxide varistor of the present invention comprises the following steps:
a)根據氧化鋅變阻器的電位梯度介於1200～9000V/mm，預製摻雜不等價離子的氧化鋅晶粒；a) according to the potential gradient of the zinc oxide varistor is between 1200 and 9000 V/mm, prefabricating the zinc oxide crystal grains of the non-equivalent ions;
b)根據氧化鋅變阻器的電位梯度介於1200～9000V/mm，預製高阻抗的燒結粉(或玻璃粉)；b) pre-fabricated high-impedance sintered powder (or glass powder) according to the potential gradient of the zinc oxide varistor between 1200 and 9000 V/mm;
c)以步驟a)的氧化鋅晶粒與步驟b)的燒結粉為原料，製備氧化鋅變阻器用的陶瓷粉；及c) preparing the ceramic powder for the zinc oxide varistor by using the zinc oxide crystal grains of the step a) and the sintered powder of the step b) as raw materials;
d)使用步驟c)的陶瓷粉，製備電位梯度介於1200～9000V/mm、非線性係數α介於21.5～55的氧化鋅變阻器。d) Using the ceramic powder of step c), prepare a zinc oxide varistor having a potential gradient between 1200 and 9000 V/mm and a nonlinear coefficient α ranging from 21.5 to 55.
在本發明製法中的步驟a)，是使氧化鋅晶粒透過不等價離子的摻雜(即，置換Zn2+ 離子或填隙)，在燒結過程可抑制氧化鋅晶體生長，而達到充分半導化。Step a) in the process of the present invention is to pass the zinc oxide crystal grains through the doping of the non-equivalent ions (ie, to replace the Zn 2+ ions or interstitial), and to inhibit the growth of the zinc oxide crystal during the sintering process, and to achieve sufficient Semi-conductive.
根據結晶學原理，氧化鋅晶粒摻雜的不等價離子，得選自由鋰(Li)、銅(Cu)、鋁(Al)、鈰(Ce)、鈷(Co)、鉻(Cr)、銦(In)、鎵(Ga)、鉬(Mo)、錳(Mn)、鈮(Nb)、鑭(La)、釔(y)、鐠(Pr)、銻(Sb)、鎳(Ni)、鈦(Ti)、釩(v)、鎢(W)、鋯(Zr)、鐵(Fe)、硼(B)、矽(Si)及錫(Sn)所組成的群體的其中一種或一種以上；而不等價離子的摻雜量得依實際情況而定，其摻雜量小於氧化鋅的20mol%。According to the crystallographic principle, the oxidized zinc crystal doped unequal ions are selected from the group consisting of lithium (Li), copper (Cu), aluminum (Al), cerium (Ce), cobalt (Co), chromium (Cr), Indium (In), gallium (Ga), molybdenum (Mo), manganese (Mn), niobium (Nb), lanthanum (La), yttrium (y), strontium (Pr), strontium (Sb), nickel (Ni), One or more of a group consisting of titanium (Ti), vanadium (v), tungsten (W), zirconium (Zr), iron (Fe), boron (B), cerium (Si), and tin (Sn); The doping amount of the non-equivalent ions is determined according to the actual situation, and the doping amount thereof is less than 20 mol% of zinc oxide.
製備氧化鋅晶粒摻雜不等價離子的方法，包括以下二種：A method for preparing zinc oxide crystal grains doped with unequal ions includes the following two types:
根據氧化鋅變阻器的指定性能，選用擬摻雜離子的可溶鹽，配製成一定濃度的水溶液，將氧化鋅粉末加入到上述溶液中經攪拌、烘乾後，再經950～1550℃煅燒，最後將燒結料經破碎、磨細至所需的細度待用。According to the specified performance of the zinc oxide varistor, the soluble salt of the pseudo-doped ion is selected to prepare a certain concentration of the aqueous solution, and the zinc oxide powder is added to the above solution, stirred, dried, and then calcined at 950 to 1550 ° C. Finally, the sinter is crushed and ground to the required fineness for use.
根據氧化鋅變阻器的指定性能，採用製備微粉的物理法或化學法奈米技術，製備含有擬摻雜離子的氧化鋅晶粒。其中，所述物理法包括氣相沉積法、激光法、微波法等；所述化學法包括沉澱法、微乳法、水熱法、相轉移法和溶膠-凝膠法等。According to the specified properties of the zinc oxide varistor, zinc oxide crystal grains containing pseudo-doped ions are prepared by physical method or chemical nanotechnology for preparing fine powder. The physical method includes a vapor deposition method, a laser method, a microwave method, and the like; and the chemical method includes a precipitation method, a microemulsion method, a hydrothermal method, a phase transfer method, and a sol-gel method.
如應用化學沉澱法，將含有鋅離子的溶液與含有摻雜離子的溶液混合經攪拌製成含有鋅離子與摻雜離子的均勻混合溶液；在攪拌條件下，採用正向或逆向加入法，將沉澱劑溶液加入上述混合溶液，經控制合適的PH值後，取得共沉澱物。對共沉澱物經過多次清洗，經烘乾後，在合適的溫度下煅燒，即可獲得含有摻雜離子的氧化鋅晶粒。If a chemical precipitation method is used, a solution containing zinc ions is mixed with a solution containing doping ions and stirred to form a homogeneous mixed solution containing zinc ions and doping ions; under stirring, a forward or reverse addition method is used. The precipitant solution is added to the above mixed solution, and after controlling a suitable pH value, a coprecipitate is obtained. After the coprecipitate is washed several times, after drying, it is calcined at a suitable temperature to obtain zinc oxide crystal grains containing doping ions.
所述的沉澱劑可選自草酸、尿素、碳酸銨、碳酸氫銨、氨水、乙醇胺或其他鹼性溶液。煅燒溫度視共沉澱物的分解溫度而定。The precipitating agent may be selected from the group consisting of oxalic acid, urea, ammonium carbonate, ammonium hydrogencarbonate, aqueous ammonia, ethanolamine or other alkaline solutions. The calcination temperature depends on the decomposition temperature of the coprecipitate.
如應用溶膠-凝膠法(Sol-Gel法)，是將鋅離子均勻分散於含擬摻雜離子的無機鹽或金屬醇鹽溶膠中，經過進行水解、聚縮反應形成溶膠後，再經固化及熱處理製得摻雜不等價離子的氧化鋅晶粒。For example, when the sol-gel method (Sol-Gel method) is applied, the zinc ions are uniformly dispersed in an inorganic salt or a metal alkoxide sol containing a pseudo-doped ion, and after being hydrolyzed and polycondensed to form a sol, and then cured. And heat treatment to obtain zinc oxide crystal grains doped with non-equivalent ions.
上述兩種奈米製備技術，可以獲得將摻雜離子成分散佈非常均勻的細小粒徑氧化鋅晶粒，而且熱處理溫度較低，介於350～1000℃，且便於大量生產。The above two nano-preparation techniques can obtain fine-grained zinc oxide crystal grains in which the doped ions are dispersed into a very uniform dispersion, and the heat treatment temperature is low, ranging from 350 to 1000 ° C, and is convenient for mass production.
本發明製法中的步驟a)與步驟b)是獨立的不同工序。在本發明製法中的步驟b)，是根據氧化鋅變阻器的性能而配製不同成份的燒結粉(或稱晶間相組分)。Step a) and step b) in the process of the present invention are separate processes. In step b) of the process of the present invention, sintered powders (or intercrystalline phase components) of different compositions are formulated according to the properties of the zinc oxide varistor.
製備高阻抗的燒結粉的方法，包括以下二種：A method of preparing a high-impedance sintered powder includes the following two types:
根據氧化鋅變阻器的指定性能，得選自含鉍(Bi)、銻(Sb)、錳(Mn)、鈷(Co)、鉻(Cr)、鎳(Ni)、鈦(Ti)、矽(Si)、鋇(Ba)、硼(B)、硒(Se)、鑭(La)、鐠(Pr)、釔(Y)、銦(In)、鋁(Al)或錫(Sn)的其中一種或一種以上的氧化物、氫氧化物、碳酸鹽、硝酸鹽或草酸鹽為原料，經充分混合後配製不同成份的燒結料原料，經過燒結再磨細至所需細度，即製成具有高阻抗性能的燒結粉；或是將原料混合後，經高溫熔解、水淬、烘乾，再磨細成燒結粉。According to the specified properties of the zinc oxide varistor, it is selected from the group consisting of bismuth (Bi), bismuth (Sb), manganese (Mn), cobalt (Co), chromium (Cr), nickel (Ni), titanium (Ti), bismuth (Si). ), one of lanthanum (Ba), boron (B), selenium (Se), lanthanum (La), praseodymium (Pr), yttrium (Y), indium (In), aluminum (Al) or tin (Sn) or One or more kinds of oxides, hydroxides, carbonates, nitrates or oxalates are used as raw materials, and after sufficiently mixing, sinter raw materials of different compositions are prepared, and after sintering, grinding to a desired fineness, that is, having a high content Sintered powder with impedance properties; or after mixing the raw materials, melting at high temperature, quenching, drying, and grinding into sintered powder.
例如，所述燒結料是氧化物原料，得選自氧化鉍(Bi2 O3 )、氧化硼(B2 O3 )、三氧化二銻(Sb2 O3 )、氧化鈷(Co2 O3 )、二氧化錳(MnO2 )、氧化鉻(Cr2 O3 )、五氧化二釩(V2 O3 )、氧化鋅(ZnO)、氧化鎳(NiO)、二氧化矽(SiO2 )或稀土氧化物等其中兩種以上的混合物。其中，所述燒結料視需要加入氧化鋅(ZnO)成份的目的，在於提升晶間相的燒結性。For example, the sinter is an oxide raw material selected from the group consisting of bismuth oxide (Bi 2 O 3 ), boron oxide (B 2 O 3 ), antimony trioxide (Sb 2 O 3 ), and cobalt oxide (Co 2 O 3 ). ), manganese dioxide (MnO 2 ), chromium oxide (Cr 2 O 3 ), vanadium pentoxide (V 2 O 3 ), zinc oxide (ZnO), nickel oxide (NiO), cerium oxide (SiO 2 ) or A mixture of two or more of rare earth oxides and the like. Among them, the purpose of adding the zinc oxide (ZnO) component to the sintered material as needed is to improve the sinterability of the intergranular phase.
根據氧化鋅變阻器的指定性能，採用物理法或化學法奈米技術製備具指定組分的奈米顆粒。本發明優選使用化學沉澱法、微乳法或溶膠-凝膠法等方法來製備具高阻抗性能的奈米顆粒。這種方法可以獲得組分均勻和粒徑細小的燒結粉。According to the specified properties of the zinc oxide varistor, the nano particles with the specified composition are prepared by physical or chemical method. The present invention preferably uses a method such as a chemical precipitation method, a microemulsion method or a sol-gel method to prepare a nanoparticle having high resistance properties. This method can obtain a sintered powder having a uniform composition and a small particle size.
在本發明製法中的步驟c)，是將步驟b)製備的高阻抗燒結粉加水製成料漿，在攪拌條件下，將一定比例的步驟a)製備的摻雜不等價離子的氧化鋅晶粒加入料漿中，經充分攪拌均勻後，經烘乾、煅燒、再磨細，即製成氧化鋅變阻器用的陶瓷粉。In the step c) of the preparation method of the present invention, the high-resistance sintered powder prepared in the step b) is added with water to form a slurry, and a certain proportion of the zinc oxide doped with the non-equivalent ion prepared in the step a) is stirred under stirring. The crystal grains are added to the slurry, and after being uniformly stirred uniformly, the ceramic powder for the zinc oxide varistor is prepared by drying, calcining, and grinding.
步驟a)的氧化鋅晶粒：步驟b)的燒結粉的重量配比，為100：2～100：50，優選100：10～100：30。The zinc oxide crystal grains of the step a): the weight ratio of the sintered powder of the step b) is from 100:2 to 100:50, preferably from 100:10 to 100:30.
在本發明製法中的步驟d)，是按習知工藝方法製成氧化鋅變阻器，包括對步驟c)的陶瓷粉製成漿料刮成生胚、印刷2層或2層以上交錯的內電極、煆燒具內電極的生胚晶粒，煆燒後，對晶粒外露內電極的兩端披覆外電極，以製得圓片型或多層片式氧化鋅變阻器。In step d) of the method of the present invention, a zinc oxide varistor is prepared according to a conventional process, and the ceramic powder of the step c) is slurried into a green body, and two or more layers of interlaced internal electrodes are printed. The raw embryonic grains of the inner electrode of the crucible are immersed, and the outer electrodes of the exposed inner electrodes are coated with the outer electrodes to obtain a wafer-type or multi-layered zinc oxide varistor.
本發明的氧化鋅變阻器製法，具有下列功效：The zinc oxide varistor manufacturing method of the invention has the following effects:
本發明製法中的步驟a)因為是獨立工序，克服了氧化鋅變阻器習知製法的缺點，在氧化鋅晶粒摻雜不等價離子的過程中，不必受所選用的高阻抗晶間相組分的限制，且具有以下優點而提高了氧化鋅晶粒之間的肖特基勢壘的高度，結果所製得的氧化鋅變阻器兼具超高電位梯度和非線性特性：Step a) in the preparation method of the present invention overcomes the shortcomings of the conventional method for the zinc oxide varistor because it is an independent process, and does not have to be subjected to the selected high-impedance intergranular phase group in the process of doping zinc oxide crystal grains with non-equivalent ions. The limitation of the fraction has the following advantages to increase the height of the Schottky barrier between the zinc oxide grains, and as a result, the obtained zinc oxide varistor has both an ultra-high potential gradient and a nonlinear characteristic:
1)擴大可供選擇的摻雜離子成分種類；1) Expand the types of dopant ion components that can be selected;
氧化鋅晶粒摻雜離子時，不受高阻抗晶間相組分的限制，大大擴展了氧化鋅晶粒能夠摻雜的不等價離子成分種類。When the zinc oxide crystal grains are doped with ions, they are not restricted by the high-resistance interphase phase component, and the types of unequal ionic components that the zinc oxide crystal grains can be doped are greatly expanded.
2)提高了不等價離子的摻雜量；2) increasing the doping amount of the unequal ions;
因為氧化鋅晶粒可以創造最佳的離子摻雜條件來摻雜不等價離子，結果氧化鋅晶粒的不等價離子摻雜量將大為提高。Since the zinc oxide grains can create optimal ion doping conditions to dope the unequal ions, the unequal ion doping amount of the zinc oxide grains will be greatly improved.
本發明的製法中，通過調整晶間相組分來抑制氧化鋅晶粒的長大，或通過超細磨工藝使氧化鋅晶粒的尺寸減小，或是選用奈米級的氧化鋅晶粒，都可以提高單位厚度的氧化鋅晶粒數量及增加晶界數，使得所製得的氧化鋅變阻器具高電位梯度和非線性特性。In the process of the present invention, the growth of the zinc oxide crystal grains is suppressed by adjusting the interphase phase composition, or the size of the zinc oxide crystal grains is reduced by an ultrafine grinding process, or a nanometer zinc oxide crystal grain is selected. Both can increase the number of zinc oxide grains per unit thickness and increase the number of grain boundaries, so that the obtained zinc oxide varistor has high potential gradient and nonlinear characteristics.
本發明製法中的步驟b)因為是獨立工序，應用奈米技術得將晶間相組分製成奈米粒徑的顆粒，且所製成的每一個顆粒均含有幾近相同的組分。更重要的是將Bi2 O3 與其他晶間相組分通過磨細、煅燒或是將所選的(包含Bi2 O3 )晶間相各組分應用奈米技術來合成，可以使每一個奈米顆粒具有含Bi2 O3 的相似組分。在燒結過程中，幾近相同結構的晶間相各組分，有助於降低Bi2 O3 融體中氧化鋅的溶解度、減少氧化鋅晶粒生長速度及抑制氧化鋅晶粒長大。所以，藉單位厚度的氧化鋅晶粒數量及晶界數的增加，所製得的氧化鋅變阻器具高電位梯度和非線性特性。Step b) in the process of the present invention is a separate process in which the interphase phase component is formed into particles having a nanometer particle size by using nanotechnology, and each of the particles produced contains nearly the same components. More importantly, Bi 2 O 3 and other interphase components can be synthesized by grinding, calcining or by using the nanotechnology of selected (including Bi 2 O 3 ) intercrystalline phase components. One nanoparticle has a similar composition containing Bi 2 O 3 . During the sintering process, the components of the intergranular phase of the same structure help to reduce the solubility of zinc oxide in the Bi 2 O 3 melt, reduce the growth rate of zinc oxide grains and inhibit the growth of zinc oxide grains. Therefore, by the increase in the number of zinc oxide grains per unit thickness and the increase in the number of grain boundaries, the zinc oxide varistor has a high potential gradient and nonlinear characteristics.
用化學沉澱法製備代號G1-10的燒結料，其組分列於表1。A sintered material of the code G1-10 was prepared by chemical precipitation, and the components thereof are shown in Table 1.
用摻雜離子溶液浸泡法來製備摻雜ZnO*晶粒，其摻雜離子種類和比例列於表2。Doped ZnO* grains were prepared by doping ion solution soaking, and the doping ion species and ratios are listed in Table 2.
選取經過不同煅燒溫度950℃、1250℃及1550℃且持溫2小時而製得的摻雜ZnO*晶粒分別與G1-10燒結料粉末混合均勻後，以1000kg/cm2 壓力分別壓製成直徑8.4mm的圓片，再以燒結溫度920℃持溫8小時，接著在800℃完成表面銀電極的燒結，製成圓片型的氧化鋅變阻器。其性能分別列於表3。The doped ZnO* grains prepared by different calcination temperatures of 950 ° C, 1250 ° C and 1550 ° C for 2 hours were uniformly mixed with G1-10 sintering powder, and then pressed into a diameter of 1000 kg/cm 2 respectively. The 8.4 mm wafer was further heated at a sintering temperature of 920 ° C for 8 hours, and then the surface silver electrode was sintered at 800 ° C to prepare a wafer-type zinc oxide varistor. Their performance is listed in Table 3.
用化學共沉澱法製備表5所列的摻雜1mol%銦(In)離子成份 的氧化鋅晶粒樣品。用化學共沉澱法製備代號G1-00的燒結料，其成份及重量比列於表4。Preparation of the doping 1 mol% indium (In) ion component listed in Table 5 by chemical coprecipitation Zinc oxide grain sample. The sintered material of code G1-00 was prepared by chemical coprecipitation method, and the composition and weight ratio thereof are shown in Table 4.
按氧化鋅晶粒樣品：G1-00燒結料的重量配比為100：10或100：15或100：30的比例混合均勻，接著以1000kg/cm2 的壓力壓製成圓片，再以燒結溫度1065℃持溫2小時，接著在800℃完成塗覆銀電極，並且製成圓片型氧化鋅變阻器。分別測量各種氧化鋅變阻器的性能，其結果詳見表5。According to the zinc oxide crystal sample: G1-00 sintering material is mixed in a ratio of 100:10 or 100:15 or 100:30, and then pressed into a pellet at a pressure of 1000 kg/cm 2 , and then sintered. The temperature was held at 1065 ° C for 2 hours, followed by completion of coating the silver electrode at 800 ° C, and a wafer-type zinc oxide varistor was prepared. The performance of various zinc oxide varistor was measured separately, and the results are shown in Table 5.
由表5可知，當氧化鋅晶粒掺雜同種掺雜離子成份時，氧化鋅變阻器的壓敏特性，將隨著氧化鋅晶粒與高阻抗燒結料的配比之不同而不同。所以，從控制氧化鋅晶粒的掺雜離子成份種類或調配氧化鋅晶粒與高阻抗燒結料的配比，可以製得電位梯度超過1700V/mm的氧化鋅變阻器。It can be seen from Table 5 that when the zinc oxide crystal grains are doped with the same doping ion component, the pressure sensitive property of the zinc oxide varistor will vary with the ratio of the zinc oxide crystal grains to the high-impedance sintering material. Therefore, a zinc oxide varistor having a potential gradient of more than 1700 V/mm can be obtained by controlling the type of the doping ion component of the zinc oxide crystal grain or by adjusting the ratio of the zinc oxide crystal grain to the high-impedance sintering material.
同實施例1，用化學沉澱法製備G1-10燒結料粉末；用摻雜 離子溶液浸泡法來製備摻雜ZnO*晶粒，且經過煅燒溫度950℃持溫2小時製得，其摻雜離子種類和比例列於表6。In the same manner as in Example 1, the G1-10 sintered powder was prepared by chemical precipitation; Ion solution immersion method was used to prepare doped ZnO* crystal grains, and the temperature was 950 ° C for 2 hours. The doping ion species and ratio are listed in Table 6.
同實施例1，將其製成圓片型的氧化鋅變阻器，其性能列於表7。其中，所製得的試樣編號1~4氧化鋅變阻器的電位梯度均超過1200V/mm、非線性特性α超過27.41及漏電流IL 低於16.5μA。尤其所製得的試樣編號4氧化鋅變阻器的電位梯度高達6023V/mm。In the same manner as in Example 1, it was made into a wafer type zinc oxide varistor, and its properties are shown in Table 7. Among them, the sample potential of the sample No. 1 to 4 zinc oxide varistor has a potential gradient exceeding 1200 V/mm, the nonlinear characteristic α exceeds 27.41, and the leakage current I L is lower than 16.5 μA. In particular, the potential gradient of the sample No. 4 zinc oxide varistor was as high as 6023 V/mm.
同實施例1，用化學沉澱法製備G1-10燒結料粉末；用溶膠-凝膠法製備摻雜ZnO*晶粒，且經過煅燒溫度350℃持溫3小時製得，其摻雜離子種類和比例分別相同於實施例3的試樣編號3 與4，試樣編號將之分別編為No 3-nm與No 4-nm，其X光繞射圖譜分別列於圖1與圖2。從摻雜ZnO*晶粒X光繞射圖譜和ZnO標準圖譜比對可知，在此低的煅燒條件下，已形成了氧化鋅的晶體。In the same manner as in the first embodiment, the G1-10 sinter powder was prepared by chemical precipitation method; the doped ZnO* crystal grains were prepared by the sol-gel method, and the calcination temperature was maintained at 350 ° C for 3 hours, and the doping ion species and The ratios are the same as those of the sample number 3 of the embodiment 3 And 4, the sample number is divided into No 3-nm and No 4-nm, and the X-ray diffraction patterns are shown in Fig. 1 and Fig. 2, respectively. From the X-ray diffraction pattern of doped ZnO* grains and the ZnO standard pattern, it is known that under this low calcination condition, crystals of zinc oxide have been formed.
同實施例1製成圓片型氧化鋅變阻器，其性能列於表8。A wafer type zinc oxide varistor was prepared in the same manner as in Example 1, and its properties are shown in Table 8.
註：崩潰電壓在6500V/mm以上的樣品，其崩潰電壓已超出儀器的量測範圍。所以，利用測繪出I-V曲線，然後用V1 (I1 =0.1mA)與V2 (I2 =1.0mA)的數值，按公式()計算出非線性係數α值；漏電流IL 按規定取80%BDV時的電流。Note: For a sample with a breakdown voltage above 6500V/mm, the breakdown voltage has exceeded the measurement range of the instrument. So, use the mapping of the IV curve, then use the values of V 1 (I 1 =0.1 mA) and V 2 (I 2 =1.0 mA), according to the formula ( Calculate the value of the nonlinear coefficient α; the leakage current I L is the current when 80% BDV is specified.
試樣編號No 3-nm的圓片試樣與No 4-nm的圓片試樣的I-V曲線圖分別為圖3與圖4。The I-V graphs of the sample No. 3-nm sample and the No 4-nm wafer sample are shown in Figs. 3 and 4, respectively.
其中，所製得的試樣編號No 3-nm及No 4-nm氧化鋅變阻器的電位梯度均超過6800V/mm。尤其所製得的試樣編號No 4-nm的氧化鋅變阻器的電位梯度超過9000V/mm、非線性特性α達到21.50及漏電流IL 低於16μA。Among them, the potential gradients of the sample No. 3-nm and No 4-nm zinc oxide varistor obtained were both over 6800 V/mm. In particular, the sample of the sample No. 4-nm zinc oxide varistor had a potential gradient of more than 9000 V/mm, a nonlinear characteristic α of 21.50, and a leakage current I L of less than 16 μA.
取實施例1中的1250℃煅燒的摻雜ZnO*與G1-10燒結料粉均勻混合，通過行星磨設備將其分別製得平均粒徑為2.1μm、 1.1μm和0.56μm的三種試樣，按實施例1製成圓片型的氧化鋅變阻器，其性能列於表9The doped ZnO* calcined at 1250 ° C in Example 1 was uniformly mixed with the G1-10 sintered powder, and the average particle diameter was 2.1 μm by a planetary milling device. Three samples of 1.1 μm and 0.56 μm were fabricated into a wafer-type zinc oxide varistor according to Example 1, and the properties thereof are shown in Table 9.
其中，氧化鋅陶瓷粉的粒徑小於1.1μm，所製得的氧化鋅變阻器的電位梯度均超過1200V/mm。所以，本實施例證實了提高氧化鋅陶瓷粉的細度，是可以提高氧化鋅變阻器的電位梯度。Wherein, the particle size of the zinc oxide ceramic powder is less than 1.1 μm, and the potential gradient of the obtained zinc oxide varistor exceeds 1200 V/mm. Therefore, this embodiment demonstrates that the fineness of the zinc oxide ceramic powder can be improved, and the potential gradient of the zinc oxide varistor can be improved.
用實施例3中的試樣編號2氧化鋅陶瓷粉，按多層晶片型變阻器的常規製法，分別製作2220與1210型多層晶片型變阻器，再經過燒結溫度900℃持溫8小時下燒成，其電性列於表10。Using the sample No. 2 zinc oxide ceramic powder of Example 3, a 2220 and 1210 type multilayer wafer type varistor was separately produced according to a conventional method of a multilayer wafer type varistor, and then fired at a sintering temperature of 900 ° C for 8 hours. The electrical properties are listed in Table 10.
其中，所製得的2220ML100與1210ML100型多層晶片型變阻器的電位梯度均超過2000V/mm及非線性特性α均超過35。Among them, the potential gradients of the 2220ML100 and 1210ML100 multilayer wafer varistor obtained both exceeded 2000V/mm and the nonlinear characteristic α exceeded 35.
用實施例3中的No 3氧化鋅陶瓷粉，按多層晶片型變阻器的常規製法，分別製作2220與1210型多層晶片型變阻器，再經過燒結溫度900℃持溫8小時下燒成，其電性列於表11。Using the No. 3 zinc oxide ceramic powder in Example 3, a 2220 and 1210 multilayer wafer type varistor was fabricated according to the conventional method of a multilayer wafer type varistor, and then fired at a sintering temperature of 900 ° C for 8 hours, and its electrical properties were obtained. Listed in Table 11.
其中，所製得的2220ML390與1210ML390型多層晶片型變阻器的電位梯度大約4000V/mm及非線性特性α均超過44。Among them, the 2220ML390 and 1210ML390 multilayer wafer varistor produced have a potential gradient of about 4000 V/mm and a nonlinear characteristic α of more than 44.
實施例6及實施例7證實了本發明製法也適用於製造兼具高電位梯度及非線性特性的多層晶片型變阻器。Example 6 and Example 7 demonstrate that the process of the present invention is also applicable to the fabrication of a multilayer wafer varistor having both high potential gradient and nonlinear characteristics.
同實施例1，用G1-10燒結料粉分別與未摻雜離子的氧化鋅晶粒和摻雜離子的氧化鋅晶粒為原料，製作圓片型氧化鋅變阻器，其性能列於表12，而且其圓片試件的電子掃描剖面圖照片分別列於圖5與圖6。In the same manner as in the first embodiment, a disk-type zinc oxide varistor was prepared by using G1-10 sinter powder and zinc oxide grains of undoped ions and zinc oxide grains doped with ions, and the properties thereof are shown in Table 12. Moreover, the electronic scanning sectional photographs of the wafer test pieces are shown in Fig. 5 and Fig. 6, respectively.
根據電子掃描剖面圖照片來測量計算，未摻雜離子的圓片試樣中，其ZnO晶粒的平均粒徑為5.2μm，而經離子摻雜的圓片試樣中，其ZnO*晶粒的平均粒徑為2.2μm，其粒徑比為2.4倍。上述兩試樣在同樣條件下燒成，但氧化鋅晶粒尺寸差2.4倍，即表明摻雜離子的氧化鋅得有效抑制氧化鋅晶粒在燒結過程中生長。According to the photograph of the electronic scanning profile, the average particle diameter of the ZnO crystal grains in the undoped ion sample is 5.2 μm, and the ZnO* crystal grains in the ion doped wafer sample. The average particle diameter was 2.2 μm, and the particle diameter ratio was 2.4 times. The above two samples were fired under the same conditions, but the zinc oxide grain size was 2.4 times different, indicating that the ion-doped zinc oxide was effective to inhibit the growth of zinc oxide grains during sintering.
而且，按單位厚度中氧化鋅晶粒數與電位梯度的公式計算，經離子摻雜的氧化鋅圓片的電位梯度應是777.6V/mm(324V/mm x 2.4)，但實測結果為1370V/mm。因此可以認為這附加提高的592.4V/mm(1370V/mm減去777.6V/mm)，應歸於離子摻雜提高氧化鋅晶界的肖特基勢壘，同樣，經離子摻雜的氧化鋅變阻器具有較大的非線性係數。Moreover, according to the formula of the number of zinc oxide crystal grains and the potential gradient in the unit thickness, the potential gradient of the ion-doped zinc oxide wafer should be 777.6 V/mm (324 V/mm x 2.4), but the measured result is 1370 V/ Mm. Therefore, it can be considered that this additional increase of 592.4V/mm (1370V/mm minus 777.6V/mm) is attributed to the Schottky barrier of ion doping to increase the zinc oxide grain boundary. Similarly, the ion doped zinc oxide varistor Has a large nonlinear coefficient.
同實施例1，用G1-10燒結料粉分別與實施例3的試樣編號3與4的摻雜ZnO*為原料製成圓片型氧化鋅變阻器，該變阻器在不同溫度下的漏電流值列於表13。In the same manner as in the first embodiment, the G1-10 sinter powder and the doped ZnO* of the sample Nos. 3 and 4 of the third embodiment were used as raw materials to prepare a wafer-type zinc oxide varistor, and the leakage current of the varistor at different temperatures was obtained. Listed in Table 13.
圖1為實施例4試樣編號No 3-mm ZnO*晶粒的X光燒射圖譜。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an X-ray burned pattern of Sample No. No. 3-mm ZnO* crystal grains of Example 4.
圖2為實施例4試樣編號No 4-nm ZnO*晶粒的X光繞射圖譜。2 is an X-ray diffraction pattern of the sample No. 4-nm ZnO* crystal grains of Example 4.
圖3為實施例4試樣編號No 3-nm圓片型氧化鋅變阻器的I-V圖。Fig. 3 is a I-V diagram of a sample No. 3-nm wafer type zinc oxide varistor of Example 4.
圖4為實施例4試樣編號No 4-nm圓片型氧化鋅變阻器的I-V圖。Fig. 4 is a I-V diagram of a sample No. 4-nm wafer type zinc oxide varistor of Example 4.
圖5為實施例8以未掺雜離子的ZnO晶粒製成圓片型氧化鋅變阻器的電子掃描剖面圖照片。Fig. 5 is a photograph showing an electron scanning sectional view of a wafer-shaped zinc oxide varistor in which Example 8 is made of ZnO crystal grains which are not doped with ions.
圖6為實施例8以掺雜離子的ZnO*晶粒製成圓片型氧化鋅變阻器的電子掃描剖面圖照片。6 is a photograph showing an electron scanning cross-sectional view of a wafer-shaped zinc oxide varistor made of ion-doped ZnO* crystal grains in Example 8.
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| TW100143801A TWI425532B (en) | 2011-11-29 | 2011-11-29 | Process for producing zno varistor with higher potential gradient and non-coefficient value |
| US13/609,508 US20130133183A1 (en) | 2011-11-29 | 2012-09-11 | Process for producing zinc oxide varistor having high potential gradient and high non-linearity coefficient |
| JP2012251407A JP2013115431A (en) | 2011-11-29 | 2012-11-15 | Method of manufacturing zinc oxide varistor with high potential gradient and high nonlinear coefficient |
| EP12193101.8A EP2599759A1 (en) | 2011-11-29 | 2012-11-16 | Process for producing zinc oxide varistor having high potential gradient and high non-linearity coefficient |
| KR1020120132497A KR101464688B1 (en) | 2011-11-29 | 2012-11-21 | Process for producing zinc oxide varistor having high potential gradient and high non-linearity coefficient |
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| EP (1) | EP2599759A1 (en) |
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| TWI778400B (en) * | 2019-08-15 | 2022-09-21 | 日商杰富意礦物股份有限公司 | Zinc oxide powder for producing zinc oxide sintered body, zinc oxide sintered body, and method of producing these |
Families Citing this family (16)
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| KR101441237B1 (en) * | 2013-03-20 | 2014-09-17 | 동의대학교 산학협력단 | Vanadium-based zinc oxide varistor and manufacturing method for the same |
| KR101968992B1 (en) * | 2015-05-04 | 2019-04-15 | 주식회사 아모텍 | Varistor ceramic and the preparing method thereof |
| JP6756484B2 (en) * | 2016-01-20 | 2020-09-16 | 株式会社日立製作所 | Voltage non-linear resistor |
| TWI605029B (en) | 2016-10-12 | 2017-11-11 | Ruthenium-free varistor composition and laminated varistor | |
| KR102454200B1 (en) * | 2017-12-14 | 2022-10-14 | 엘티메탈 주식회사 | Manufacturing method of Indium-Tin-Oxide powder and Indium-Tin-Oxide powder using it |
| JP2021522673A (en) * | 2018-04-17 | 2021-08-30 | エイブイエックス コーポレイション | Varistor for high temperature applications |
| CN108875249B (en) * | 2018-07-02 | 2023-06-30 | 国网湖南省电力有限公司 | Formula optimization design method and device for zinc oxide resistor disc |
| CN109987933B (en) * | 2019-04-01 | 2021-11-02 | 中国科学院上海硅酸盐研究所 | Bi, Pr and V-free high-gradient ZnO voltage-sensitive ceramic material and preparation method thereof |
| CN110797395A (en) * | 2019-09-18 | 2020-02-14 | 华南理工大学 | Doped metal oxide semiconductor, thin film transistor and application |
| CN111205084A (en) * | 2020-01-19 | 2020-05-29 | 常州市创捷防雷电子有限公司 | Preparation method of silicon oxide coated modified ZnO voltage-sensitive ceramic material |
| CN111285676B (en) * | 2020-02-24 | 2021-03-30 | 武汉理工大学 | Zinc oxide pressure-sensitive ceramic material and preparation method thereof |
| CN111816398B (en) * | 2020-06-23 | 2022-01-07 | 上海大学 | Resistor disc preparation method capable of improving high-current impact stability |
| CN114605143B (en) * | 2022-03-28 | 2023-04-11 | 华中科技大学 | Based on ZnO @ SiO 2 Zinc oxide piezoresistor with core-shell structure and preparation method thereof |
| CN114907111A (en) * | 2022-05-07 | 2022-08-16 | 吉林昱丰电气科技有限公司 | High-energy high-residual-voltage-ratio nonlinear device and preparation method thereof |
| CN115385682B (en) * | 2022-08-30 | 2023-05-16 | 重庆大学 | Ultrahigh-potential gradient ZnO voltage-sensitive ceramic and low-carbon sintering preparation process thereof |
| CN116120052A (en) * | 2023-02-21 | 2023-05-16 | 哈尔滨理工大学 | Zinc oxide-based giant dielectric ceramic material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6184770B1 (en) * | 1998-04-07 | 2001-02-06 | Murata Manufacturing Co., Ltd. | Monolithic varistor |
| CN101630553B (en) * | 2009-07-17 | 2011-10-12 | 立昌先进科技股份有限公司 | Preparation method of zinc oxide varister |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920005155B1 (en) * | 1989-12-19 | 1992-06-27 | 한국 과학기술연구원 | Zno-varistor making method |
| JPH0685363B2 (en) * | 1991-09-30 | 1994-10-26 | ソマール株式会社 | High voltage varistor and manufacturing method thereof |
| KR950007948B1 (en) * | 1992-10-23 | 1995-07-21 | 서울대학교공과대학교육연구재단 | Varister |
| GB9600819D0 (en) * | 1996-01-16 | 1996-03-20 | Raychem Gmbh | Electrical stress control |
| JP3908611B2 (en) * | 2002-06-25 | 2007-04-25 | Ｔｄｋ株式会社 | Voltage nonlinear resistor ceramic composition and electronic component |
| US20090142590A1 (en) * | 2007-12-03 | 2009-06-04 | General Electric Company | Composition and method |
| TWI402864B (en) * | 2008-07-11 | 2013-07-21 | Sfi Electronics Technology Inc | A method of making zinc oxide varistor |
| KR101161924B1 (en) * | 2009-08-27 | 2012-07-03 | 한국세라믹기술원 | ZnO-based varistor composition |
-
2011
- 2011-11-29 TW TW100143801A patent/TWI425532B/en active
-
2012
- 2012-09-11 US US13/609,508 patent/US20130133183A1/en not_active Abandoned
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- 2012-11-16 EP EP12193101.8A patent/EP2599759A1/en not_active Withdrawn
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6184770B1 (en) * | 1998-04-07 | 2001-02-06 | Murata Manufacturing Co., Ltd. | Monolithic varistor |
| CN101630553B (en) * | 2009-07-17 | 2011-10-12 | 立昌先进科技股份有限公司 | Preparation method of zinc oxide varister |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI778400B (en) * | 2019-08-15 | 2022-09-21 | 日商杰富意礦物股份有限公司 | Zinc oxide powder for producing zinc oxide sintered body, zinc oxide sintered body, and method of producing these |
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| JP2013115431A (en) | 2013-06-10 |
| EP2599759A1 (en) | 2013-06-05 |
| TW201212051A (en) | 2012-03-16 |
| US20130133183A1 (en) | 2013-05-30 |
| KR101464688B1 (en) | 2014-11-27 |
| KR20130060127A (en) | 2013-06-07 |
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